Carboxylation of acetylenic compounds

ABSTRACT

Method of carboxylating an organic compound of the group of RC*CH, RCH2CN, indene or cyclopentadiene where R is hydrocarbyl comprising contacting under anhydrous conditions in an inert atmosphere and in the presence of an inert, aprotic, dipolar, liquid solvent, said compound with a carbonated metal phenoxide, the metal phenoxide of the formula: WHERE X is sodium or potassium, R1 is hydrogen or alkyl, and subsequently acidifying the resultant intermediate product to form the carboxylated product.

United States Patent Patmore et al.

CARBOXYLATION OF ACETYLENIC COMPOUNDS Inventors: Edwin L. Patmore; William R. Siegart; Harry Chafetz, all of c/o Texaco lnc. PO. Box 509, Beacon, NY. 12508 Filed: Nov. 10, 1971 Appl. No.: 197,530

Related US. Application Data Division of Ser. No. 794,344, Jan. 27, 1969.

US. Cl. ..260/515 R, 260/413, 260/533 A Int. Cl. ..C07c 53/00, C07c 63/00 Field of Search ..260/515 R, 533 A, 413

References Cited UNITED STATES PATENTS l/1957 Neuman et a1 ..260/533 A 9/1960 Frank et a1 ..260/515 R 9/1966 Kurtz ..260/515 R 7/1971 Patmore et a] ..260/533 A Primary Examiner-James A. Patten Attorney-K. E. Kavanagh et a1.

[57] ABSTRACT where X is sodium or potassium, R is hydrogen or alkyl, and subsequently acidifying the resultant intermediate product to form the carboxylated product.

5 Claims, No Drawings CARBOXYLATION OF ACETYLENIC COMPOUNDS This is a division, of application Ser. No. 794,344 filed Jan. 27, 1969.

BACKGROUND OF INVENTION The subject invention is found in the field of art relating to the introduction of a carboxylic acid group into organic compounds. In the past, in order to carboxylate the starting compounds contemplated herein utilizing carbon dioxide the contacting had to be accomplished in the presence of relatively expensive bases such as sodium, naphthalene, n-butyl lithium and sodium hydride. Due to the cost of the base, the prior art methods of carboxylating the reactants contemplated herein had only limited commercial prospects.

SUMMARY OF INVENTION We have discovered a method of carboxylating organic compounds of the group of RC CH, RCI-1 CN, indene or cyclopentadiene where R is alkyl, aryl, a1-

between 1 and 200 atmospheres and in an inert atmosphere utilizing a mole ratio of said carbonated metal phenoxide to'said organic reactant of between about 2:1 and :1 and subsequently acidifying the resultant mixture to respectively form carboxyl compounds of the group of lt( (l()0I-I, RdHoN,

indene-3-carboxylic acid and tricyclo[5.2.1.0]deca- 3,8-diene-4,9-dicarboxylic acid. The carbonated metal phenoxide is prepared by contacting with an excess of carbon dioxide a metal phenoxide of the formula:

karyl and aralkyl of from one to 20 carbons consisting essentially of contacting said organic compounds under anhydrous conditions in an inert atmosphere and in the presence of an inert, aprotic, dipolar, liquid solvent with the reaction product of carbon dioxide and a base of the formula:

where X is sodium or potassium and R is hydrogen or alkyl or from one to 12 carbons and subsequently acidifying the resultant reaction mixture to recover the carboxylic acid product.

The discovery that the carbonated metal phenoxide salts facilitate the production of carboxylated products in high yields has rendered a base catalyzed carboxylation process for the starting materials contemplated herein commercially feasible since the carbonated phenoxide is many times less expensive than previous bases employed. Further, the subject method has several advantages over the method set forth in our coassigned, copending application Ser. No. 784,901, filed Dec. 12, 1968, now matured to U.S. Pat. No. 3,595,907, wherein carboxylation occurs by contacting the organic reactant with carbon dioxide in the presence of uncarbonated metal phenoxide followed by acidification. These several advantages are a substantial reduction in the amount of carbon dioxide required, a better control of the reaction and with some reactants superior yields.

DETAILED DESCRIPTION OF THE INVENTION Specifically, the invention relates to contacting under anhydrous conditions and in an inert atmosphere where X and R are as heretofore defined at a temperature between about 0 and 150 C. under a carbon dioxide pressure of between about 1 and 200 atmospheres and in the presence of inert aprotic, dipolar, liquid solvent. The reaction of the organic reactant and carbonated phenoxide under referred conditions takes place at a temperature between 25 and 50 C., at a carbon dioxide pressure of between 1 and 25 atmospheres utilizing a mole ratio of said carbonated phenoxide to said organic compound of between about 4:1 and 10: 1. By the term excess of carbon dioxide to metal phenoxide it is hereinbefore and hereinafter intended to denote a mole ratio of at least about 2:1 and up to :1 and more.

The preparation of the carbonated metal phenoxide reactant under preferred conditions takes place at a temperature between 25 and 50 C., a carbon dioxide pressure between 1 and 25 atmospheres, a mole ratio of carbon dioxide to phenoxide of between about 2:1 and 10:1 and in the presence of an inert, aprotic, dipolar, liquid solvent.

Acidification desirably takes place at a temperature between about 5 and 35 C. to a pH between about 1 and 3 to convert the intermediate product to the desired carboxylic acid derivative. A pl-I up to about 6 is also suitable.

The carboxylic acid products are recovered from the acidifiedmixture by standard means such as selective extraction, distillation, decantation and combinations thereof.

By the term anhydrous a water content less than 0.5 wt. percent is intended.

The carbonated metal phenoxide reactant is in essence a complex mixture of the phenyl carbonate salt (I) represented by the formula:

the complex of the phenoxide salt with carbon dioxide (II) represented by the formula:

n and an unidentified material lll where X and R are as heretofore defined. Compounds l and III are in nearly equal amounts and were present in slightly larger amounts than Compound II.

Examples of the organic reactant compounds contemplated herein are phenylacetylene, benzyl cyanide, acetonitrile, hexane-nitrile, acetylene, l-butyne and lhexyne.

Examples of the carbonated reactants are the carbonated sodium and potassium salts of phenol, methylphenol, t-octylphenol, nonylphenol and dodecylphenol.

Specific examples of the acidifying acids contemplated herein are the mineral acids such as hydrochloric acid, nitric acid, sulfuric acid and hydrobromic acid in aqueous concentrations ranging from 4 to 96 wt. percent.

Specific examples of the liquid solvents contem plated herein for the preparation of the carbonated phenoxide salt and the carbonated salt-organic reactant intermediate product are N,N-dimethylformamide, hexamethylphosphoramide, dimethyl sulfoxide, diphenyl sulfoxide, dimethyl sulfone and N,N-dimethyl acetamide. The quantity of solvent employed advantageously constitutes between about 50 to 90 weight percent of the reaction mixture. Further, any inert, aprotic, dipolar, liquid (under conditions of reaction solvent is suitable.

Examples of gases which can form the inert atmosphere are nitrogen, helium and argon.

Specific examples of the carboxylic acid products contemplated herein are indene-3-carboxylic acid, tricycle-[5.2.1.0 ]deca-3 ,8-diene-4,9-dicarboxylic acid, phenylpropiolic acid, alpha-phenylcyanoacetic acid, alpha-cyanohexoic acid, 2-butynoic acid, 2- propynoic acid and 2-hexynoic acid.

One of the important aspects of the method of the invention is the maintenance of anhydrous conditions during the preparation of the carbonated phenoxide salt and the carbonated salt-organic reactant intermediate. If such conditions are not observed, little or no yield of salt reactant and intermediate are obtained resulting in no yield of desired carboxylic product. Another important aspect of the method of the invention is the employment of a carbonated phenoxide salt to organic reactant of at least about 2: l. Lesser ratios result in little or no carboxylic product.

The following examples further illustrate the invention but are not to be considered as limitations thereof.

EXAMPLE I This example illustrates the preparation of alphaphenylcyanoacetic acid from benzyl cyanide.

Sodium phenoxide (25.6 grams, 0.24 mole) and dimethyl-formamide (100 mls.) were charged to a 3- necked, 250 mls. flask equipped with a magnetic stirring bar, thermometer, gas sparger and water cooled condenser fitted with an expansion bulb. The exit of the expansion bulb was connected to a mercury bubbler to protect the system from the atmosphere. Dry carbon dioxide was bubbled into the clear brown solution. The temperature rose from 33 to 46 C. and the contents of the flask became a milky, grey-brown mixture. After 20 minutes the temperature dropped to 34 C. Foaming was observed at this point. Excess carbon dioxide was bubbled into the solution and after approximately an hour the mixture started to clear and the solids dissolved. Carbon dioxide was passed into the reaction mixture for a total of 3 hours. Carbon dioxide blowing was discontinued and replaced by a stream of dry nitrogen(sequentially passed through concentrated sulfuric acid and then soda lime). Benzyl cyanide (7 grams, 0.06 mole) was charged to the flask with an additional l5 mls. of dimethyl-formamide. The mixture was stirred for 3 hours under nitrogen. The nitrogen was removed and the system closed and the mixture allowed to stand overnight.

The reaction mixture was poured into a beaker containing 100 grams of ice and 100 mls. of concentrated HCl. The aqueous acidic layer was extracted with ether (6Xl00 mls.). The combined ether layers were extracted with 10 percent sodium bicarbonated (5 l00 mls.). The bicarbonate extracts were cooled in an ice bath and made acidic with 6 molar hydrochloric acid. The acidified solution was extracted with ether( 6x100 mls.). The combined ether extracts were washed with water mls.) and dried over anhydrous sodium sulfonate and over anhydrous calcium sulfate. The solution was filtered and the ether removed on the rotary evaporator to give 7.5 grams of acidic material which solidified upon standing. An infrared spectral analysis confirmed the product as alpha-phenyl-cyanoacetic acid.

The crude alpha-phenylcyanoacetic acid was recrystallized from 55 mls. of benzene and 150 mls. of petroleum ether and the yield of purified acetic acid product was determined to be 64 mole percent. Elemental analysis of the recrystallized product gave the following: Found: wt. C 66.9; wt. H 4.4; wt. N-8.4;Calc: wt. %C=67;wt. %H=4.3;wt. N 8.69.

The reactions of the above were conducted under atmospheric pressure.

EXAMPLE II EXAMPLE III This example illustrates the criticality of maintaining an anhydrous reaction basically utilizing the general method and apparatus set forth in Example I with the following exceptions: Carbon dioxide was bubbled into a solution of sodium phenoxide (28.3 grams, 0.24 mole) and dimethylformamide mls.) for 10 minutes. Then several drops of water about (0.09 grams) were added and an immediate cloudiness followed by a solid formation was observed. Carbon dioxide flow was maintained for a total of 3 hours. Carbon dioxide was discontinued, benzyl cyanide (7 grams, 0.06 mole) was added and the system closed to the atmosphere. The mixture was allowed to stir for approximately 3 hours and then allowed to stand overnight. The reaction mixture was then acidified and worked up. No carboxylic acid product was recovered.

EXAMPLE IV This example illustrates the desirability of having an extended reaction time between'the sodium phenoxide and carbon dioxide to form the carbonated intermediate.

The procedure employed was essentially that of Example I. The reactive carboxylated phenoxide was prepared by bubbling an excess of carbon dioxide into a solution of sodium phenoxide (13.9 grams, 0.12 mole) and dimethylformamide (75 mls.) for approximately 24 minutes rather than the 3 hour period in Example l (3246 C.). The carbon dioxide stream was then discontinued and the sparger replaced by a plug. Then benzyl cyanide (3.5 grams, 0.03 mole) was added and the mixture was stirred for 3 hours. The mixture was allowed to stand overnight, acidified and worked up to give a crude acidic product which was recrystallized from benzene (35 mls.)-petroleum ether (75 mls.) to give 2.43 grams alpha-phenylcyanoacetic acid in a yield of 50 percent which is somewhat less than the 64 percent yield of Example I.

EXAMPLE V This example illustrates the preparation of phenylpropiolic acid from phenylacetylene.

Utilizing the general procedure and apparatus described in Example I with the following changes:

Carbon dioxide was bubbled into a solution of sodium phenoxide (13.0 grams, 0.12 mole) and dimethylformamide (75 mls.) for 3 hours at 2835 C. Then phenylacetylene (6.2 grams, 0.06 mole) under nitrogen was added and the mixture stirred 3 hours under nitrogen. The nitrogen stream was discontinued, the system closed to the atmosphere, and the reaction mixture allowed to stand overnight. The product mixture was acidified and worked up to give 2 grams of crude phenylpropiolic acid representing a mole percent yield of 23. A recrystallized sample of phenylpropiolic acid (from distilled water) ga've white crystals, m.p. 136-l3 7 and elemental analysis gave the following: Found: wt. C 74.0, wt. H 4.4; Calc.: wt. C 73.97, wt. H 4.1.

EXAMPLE VI This example further illustrates the preparation of phenylpropiolic acid from phenylacetylene and when the yield is compared to Example V this demonstrates the preferability of a 4:1 ratio of carbonated phenoxide to phenylacetylene reactant as opposed to the 2:1 ratio used in Example V.

The procedure of Example V was essentially re peated with the exception that the carbonated intermediate was formed by the reacting 27.8 grams (0.24

mole) of sodium phenoxide with excess carbon dioxide in mls. dimethylformamide. In the subsequent reaction of the carbonated intermediate 6.2 grams (0.06 mole) of phenylacetylene was employed. Phenylpropiolic acid in an amount of 4.5 grams was recovered representing a yield of 51 percent or more than double that of Example V.

EXAMPLE VII This example illustrates the preparation of indene-3- carboxylic acid from indene.

The procedure and apparatus employed was that in general described in Example I. The carboxylated sodium phenoxide intermediate was prepared by bubbling excess carbon dioxide into a solution of sodium phenoxide (13.9 grams, 0.12 mole) and dimethylformamide (100 mls.) for 3 hours. The temperature ranged from 20 to 38 C. The carbon dioxide was replaced by dry nitrogen. Then indene (3.5 grams, 0.03 mole) was added and the mixture stirred for approximately 3 hours under nitrogen. The nitrogen flow was discontinued, the system closed to the atmosphere, and the reaction mixture allowed to stand overnight. The mixture was acidified and was worked up to give 4.7 grams of crude acidic material.

The crude acidic material was recrystallized from benzene to give 1.65 grams of a product whose infrared and nuclear magnetic resonance spectra were comparable to those of indene-S-carboxylic acid. This represented a yield of 34 mole percent. Elemental analysis of the recovered indene-3-carboxylic acid Found: wt. %C-75;wt. %H5;Calc.: wt. %C-75;wt. H 5.

EXAMPLE VIII This example illustrates the preparation of Thieles acid, that is, tricyclo[5.2.l.0 ]deca-3,8-diene-4,9- dicarboxylic acid.

The procedure and apparatus broadly was that employed in Example I. Carbon dioxide was bubbled into a solution of sodium phenoxide (13.9 grams, 0.12 mole) and dimethylformamide(75 mls.) for 3 hours to prepare the reactive carboxylated phenoxide. The temperature ranged from 2l42 C. The carbon dioxide stream was discontinued, the system was closed to the atmosphere and cyclopentadiene (4 grams, 0.06 mole) was added. The mixture was stirred for 3 hours and washed to give 2.5 grams of Thieles acid having a melting point of l9l-l93 C. The product was confirmed by infrared analysis. The yield basis cyclopentadiene was 38 mole percent.

We claim:

1. A method of producing a carboxylic acid compound characterized by the formula RO E CCOOH where R is alkyl, aryl, alkaryl and aralkyl of from one to 20 carbons comprising contacting a carbonated metal phenoxide with an organic reactant characterized by the formula R-C 5 CH Where R is as heretofore defined under anhydrous conditions and an inert atmosphere in a mole ratio of said carbonated phenoxide to said organic reactant of between about 2:1 and 20:1 at a temperature between about 0 and C. under a pressure of between about I and 200 atmospheres, subsequently acidifying the resultant reaction product to a pH of less than about 6 and recovering said carboxylic acid compound from the acidified mixture, said carbonated phenoxide being prepared by contacting under anhydrous conditions a base of the formula:

where X is sodium or potassium and R is hydrogen or alkyl of from one to l2 carbons with carbon dioxide in a mole ratio of carbon dioxide to said base of at least about 2:] under carbon dioxide pressure of between about 1 and 200 atmospheres, and both said contacting steps being conducted in the presence of an inert,

aprotic, dipolar, liquid solvent.

2. A method in accordance with claim 1 wherein said solvent is present in an amount between about 50 and wt. percent of the reaction mixture.

3. A method in accordance with claim 2 wherein said acidifying is conducted to a pH of between about I and mg I UNITED STATES PATENT owner QERTWECATE @F QQRREQTWN Patent 2.6961 16 Dated October 3, 1972 Inventor(s) Edwin L. "Patmore, William R. Siegart, Harry Chafetz It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

@ l I w ABSTRACT, line 2, "RC CH" should read RCECH--;

Column 1, line 39, I "or" should read -of--;

Column 1, line 51, "12" should read --18--;

Column 2, line 28; "referred" should read -preferred-;

Column 6, line- 55, "RO CCOOH" should read --R-CECCOOH-.

Signed and sealed this 20th day of November 1973.

(SEAL) Attest:

EDWARD M.FLE'1CHER',JR.' RENE Do TEGTMEYER Attesting Officer Acting Commissioner of Patents 

2. A method in accordance with claim 1 wherein said solvent is present in an amount between about 50 and 90 wt. percent of the reaction mixture.
 3. A method in accordance with claim 2 wherein said acidifying is conducted to a pH of between about 1 and
 3. 4. A method in accordance with claim 3 wherein said solvent is dimethylformamide and acidifying is conducted with hydrochloric acid.
 5. A method in accordance with claim 4 wherein said organic compound is phenylacetylene, said base is sodium phenoxide and said carboxylic acid compound is phenyl-propiolic acid. 